CN107936173B - Hydrophobic association type cationic polyacrylamide and preparation method and application thereof - Google Patents
Hydrophobic association type cationic polyacrylamide and preparation method and application thereof Download PDFInfo
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 46
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 45
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 45
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 claims abstract description 32
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 18
- 239000011737 fluorine Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 13
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000008394 flocculating agent Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulphite Substances [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 5
- 229940073608 benzyl chloride Drugs 0.000 claims description 4
- 230000033116 oxidation-reduction process Effects 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 3
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 3
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical group FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- AIBUHXJSZPPYQC-UHFFFAOYSA-M dimethyl-(1-phenylethyl)-(2-prop-2-enoyloxyethyl)azanium chloride Chemical compound [Cl-].CC(C1=CC=CC=C1)[N+](C)(C)CCOC(C=C)=O AIBUHXJSZPPYQC-UHFFFAOYSA-M 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012966 redox initiator Substances 0.000 claims 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 239000010865 sewage Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 52
- 229920000642 polymer Polymers 0.000 description 27
- 239000000243 solution Substances 0.000 description 26
- 238000010521 absorption reaction Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- 238000001035 drying Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 8
- 238000005189 flocculation Methods 0.000 description 7
- 230000016615 flocculation Effects 0.000 description 7
- 239000000693 micelle Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 125000001165 hydrophobic group Chemical group 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a hydrophobic association type cationic polyacrylamide, and a preparation method and application thereof, wherein the hydrophobic association type cationic polyacrylamide is obtained by reacting a reaction system containing a fluorine-containing monomer, methacryloyloxyethyl dimethyl benzyl ammonium chloride, acrylamide, deionized water and an initiator, wherein the mass ratio of the fluorine-containing monomer to the methacryloyloxyethyl dimethyl benzyl ammonium chloride to the acrylamide to the deionized water is 1: (1-10): (5-15): (15-40), wherein the initiator accounts for 0.5-3% of the total mass of the monomers. The hydrophobic association type cationic polyacrylamide has stronger adsorption capacity and can be better suitable for sewage treatment or impurity removal in the field of industrial production.
Description
Technical Field
The invention belongs to the field of functional high molecular polymers, relates to a synthesis method of a water-soluble high molecular polymer, and particularly relates to hydrophobic association type cationic polyacrylamide as well as a preparation method and application thereof.
Background
A surface-active monomer, also known as a polymerizable surfactant, is a functional surfactant, the particular molecular structure of which imparts unique physicochemical properties. The amphipathy of the structure can be used as a surfactant and can also be used as a monomer for polymerization, and meanwhile, the surface active monomer can be self-assembled in a solution to form various ordered assemblies, such as micelles, vesicles, lyotropic liquid crystals and the like, so that the surface active monomer has wide application in many scientific and technical fields.
Polyacrylamides can be classified by the degree of ionization into anionic, cationic, nonionic, and amphoteric. Since most of the colloidal particles in sewage are negatively charged, cationic flocculants are the main products in the market. The cationic flocculant is a water-soluble high-molecular polymer with a positive charge active group on a molecular chain, and can play roles of electrical neutralization, adsorption bridging and the like with particles in water, so that the particles in the water are destabilized and flocculated to be conductive to sedimentation, filtration and dehydration. Has the advantages of less consumption, low cost of wastewater or sludge treatment, low toxicity, wide range of use values and the like. The cationic polyacrylamide is a linear molecular polymer, can be used for treating various waste water and sewage, and is an important direction for developing cationic flocculants in China.
The hydrophobic association polyacrylamide enhances the adsorption bridging capacity between the polymer and the solid particles due to strong intermolecular hydrophobic association, and has good flocculation effect. If the cationic hydrophobic association polyacrylamide terpolymer is prepared by carrying out micelle copolymerization on the hydrophobic monomer, Acrylamide (AM) and a cationic monomer (DMC or DADMAC and the like), the cationic hydrophobic association polyacrylamide terpolymer has better flocculation effect under the combined action of electrostatic interaction and hydrophobic association bridging.
In the micelle polymerization research of recent years, a surface active monomer which does not need an additional auxiliary agent and has a self-assembly function is sought to replace a common hydrophobic monomer to prepare the water-soluble hydrophobic association polymer through a novel micro-multiphase copolymerization system. Researchers also solubilize hydrophobic monomers with surface active monomers to prepare hydrophobically associating polyacrylamide, and further increase the hydrophobic content of the polymer, so that the polymer has better hydrophobic associating capacity. However, hydrophobic associations do not meet the market demands at present.
Disclosure of Invention
The invention aims to provide hydrophobic association type cationic polyacrylamide as well as a preparation method and application thereof. The hydrophobic cationic surface active monomer can replace a surfactant in micelle polymerization, and the surface active monomer is used for solubilizing the fluorine-containing hydrophobic monomer, so that the hydrophobic association effect is enhanced, the adsorption capacity is stronger, and the method can be better suitable for sewage treatment or impurity removal in the field of industrial production.
In order to achieve the purpose, the invention adopts the technical scheme that:
the hydrophobic association type cationic polyacrylamide is obtained by reacting a reaction system containing a fluorine-containing monomer, methacryloyloxyethyl dimethylbenzyl ammonium chloride, acrylamide, deionized water and an initiator, wherein the mass ratio of the fluorine-containing monomer to the methacryloyloxyethyl dimethylbenzyl ammonium chloride to the acrylamide to the deionized water is 1: (1-10): (5-15): (15-40), wherein the initiator accounts for 0.5-3% of the total mass of the monomers.
The fluorine-containing monomer is trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate or dodecafluoroheptyl methacrylate.
The initiator is ammonium persulfate, potassium persulfate or oxidation-reduction initiator; the oxidation-reduction initiator is ammonium persulfate-sodium sulfite, ammonium persulfate-sodium bisulfite, potassium persulfate-sodium sulfite, potassium persulfate-sodium bisulfite, ammonium persulfate-sodium thiosulfate or potassium persulfate-sodium thiosulfate.
The mass ratio of the oxidant to the reducing agent in the oxidation-reduction initiation system is 3: 2.
a preparation method of hydrophobic association type cationic polyacrylamide comprises the following steps:
(1) adding a fluorine-containing monomer, methacryloyloxyethyl dimethyl benzyl ammonium chloride, acrylamide and deionized water into a reaction device provided with a stirrer and a spherical condenser pipe;
(2) filling nitrogen into the reaction device, completely removing air in the reaction device, and heating and stirring;
(3) when the temperature is raised to 40-80 ℃, an initiator is dripped to initiate polymerization reaction, and the reaction is stopped after heating reflux reaction until the reaction viscosity is not changed;
(4) taking out the product, and carrying out post-treatment to obtain the hydrophobic association type cationic polyacrylamide.
The preparation method of the methacryloyloxyethyl dimethyl benzyl ammonium chloride comprises the following steps:
adding acetone and benzyl chloride into a container, slowly dripping dimethylaminoethyl methacrylate at room temperature, wherein the molar ratio of the acetone to the benzyl chloride to the dimethylaminoethyl methacrylate is (1-3): (0.5-2.5)：(0.5-2.5)Stirring overnight, and filtering to obtain white solid; washing with acetone for several times, and vacuum drying to obtain white powder, i.e. methyl acryloyloxyethyl dimethyl benzyl ammonium chloride.
The nitrogen is liquid nitrogen or gaseous nitrogen.
Heating reflux reaction time is 3-6 h.
The post-treatment steps are specifically as follows: using a mixture of 1: 1, mixing ethanol and acetone to wash the product until the solution is clear, putting the washed product into a vacuum oven to be dried, and then grinding.
An application of hydrophobic association type cationic polyacrylamide as a flocculating agent in sewage treatment or impurity removal.
Compared with the prior art, the invention has the following advantages:
according to the product, a hydrophobic cationic surface active monomer replaces a surfactant in micelle polymerization, the surface active monomer is used for solubilizing a fluorine-containing monomer, a ternary polymerization method is adopted to prepare the hydrophobic association type cationic polyacrylamide copolymer, and the fluorine-containing monomer is solubilized by the surface active monomer of methacryloyloxyethyl dimethyl benzyl ammonium chloride, so that the fluorine-containing hydrophobic groups on a molecular chain can be aggregated, so that polymer molecules generate reversible physical association with certain strength among the molecules in an aqueous solution due to the action of static electricity, hydrogen bonds or van der Waals force. At low concentration, the hydrophobic groups in a single molecule are associated in the molecule; the concentration is increased to a certain value, intermolecular association occurs between hydrophobic groups of different molecules, and the concentration is called critical association concentration. After the concentration is reached, the molecules are gradually associated into an aggregate structure to form a huge three-dimensional network structure, and the apparent viscosity of the solution is greatly increased. Even when the concentration of the polymer solution is low, the system still has high apparent viscosity, and unlike the polyacrylamide solution, the high-efficiency viscosity increasing is realized by only increasing the relative molecular mass of the polymer. By introducing fluorine-containing hydrophobic groups, the flocculation time can be shortened, and the flocculation effect is improved. The fluorine-containing monomer is a strong hydrophobic monomer, the hydrophobic association effect of the fluorine-containing monomer is stronger than that of a hydrocarbon hydrophobic monomer, and the prepared fluorine-containing polyacrylamide copolymer has a better application effect. And avoids the treatment of residual small molecule surfactant in the post-treatment process during the polymerization of the micelle by using the surface active monomer.
The method adopts a ternary polymerization method to prepare the hydrophobic association type cationic polyacrylamide copolymer, has simple preparation process, is convenient to operate, and has easy control of the preparation process of the product. And the cationic degree of the copolymer can be changed by adjusting the composition of the raw materials, so that the prepared copolymer can be used as a novel flocculating agent.
The copolymer prepared by the invention can be used as a novel flocculant and can be better suitable for sewage treatment or impurity removal in the field of industrial production. When used as a flocculant, the flocculant has better adsorption effect than a polyacrylamide copolymer prepared from a hydrocarbon hydrophobic monomer.
Drawings
FIG. 1 is an infrared spectrum of methacryloyloxyethyl dimethylbenzyl ammonium chloride (DMBAC);
FIG. 2 is an infrared spectrum of Acrylamide (AM)/methacryloyloxyethyl dimethylbenzyl ammonium chloride (DMBAC)/trifluoroethyl methacrylate (TFEMA) polymer.
FIG. 3 is a graph of the surface tension of a polymer at various concentrations.
FIG. 4 shows the effect of polymer dosage on zeta potential of diatomaceous earth suspension supernatant.
FIG. 5 is a graph showing the effect of polymer dosage on the transmittance of the supernatant of a diatomaceous earth suspension.
FIG. 6 shows the effect of polymer addition on oil removal.
Detailed Description
The following detailed description of the present invention will be given with reference to specific examples, but the present invention is not limited to the examples. In the following description of the preferred embodiments of the present invention, specific details are set forth in order to provide a thorough understanding of the present invention.
Example 1
(1) 2mol of acetone and1mol ofBenzyl chloride, slowly dripping 1mol of dimethylaminoethyl methacrylate at room temperature, stirring overnight, and filtering to obtain a white solid; washing with acetone for several times, and vacuum drying to obtain white powdery solid, namely methacryloyloxyethyl dimethyl benzyl ammonium chloride;
(2) in a three-neck flask with a stirrer and a spherical condenser, the mass ratio of the three-neck flask to the spherical condenser is 1: 5: 7: 30 percent of trifluoroethyl methacrylate, methacryloyloxyethyl dimethylbenzyl ammonium chloride, acrylamide and deionized water.
(3) Charging high-purity nitrogen into the reaction device, completely removing air in the reaction device after 0.5h, heating and stirring.
(4) A mixed solution of ammonium persulfate and sodium bisulfite (mass ratio: 3: 2) in an amount of 1.5% by mass of the total monomers was added dropwise at 55 ℃ using a constant pressure dropping funnel. Heating and refluxing for 4 hours until the reaction viscosity does not change any more, and stopping the reaction.
(5) Taking out the product, and mixing the product with a mixture of 1: 1, mixing the washing solution with ethanol and acetone until the solution is clear, putting the washed product into a vacuum oven for drying, and grinding the obtained product to obtain the final target product, namely the hydrophobic association type cationic polyacrylamide.
As can be seen from FIG. 1, it is found that the distance between the two electrodes is 1726cm-1Is located at 1168cm and has an ester carbonyl absorption peak-1Is an absorption peak of an ester group carbon-oxygen bond; at 1637cm-1The absorption peak of the double bond is 3088cm-1Telescopic vibration absorption with CH ═ CH-HPeak at 1411cm-1，890cm-1The positions are respectively a double-bond carbon-hydrogen in-plane stretching vibration absorption peak and an out-of-plane bending vibration absorption peak; at 1294cm-1，1045cm-1The position is a stretching vibration absorption peak of a carbon-nitrogen bond in a quaternary ammonium group; at 1594cm-1，1575cm-1，1506cm-1，1429cm-1The vibration absorption peak of benzene ring skeleton is in 1218cm-1And 1000cm-1The in-plane bending vibration absorption peak of the carbon-hydrogen bond on the benzene ring is at 941cm-1The out-of-plane bending vibration absorption peak vibration of the carbon-hydrogen bond on the benzene ring; at 2981cm-1Is provided with CH3Upper C-H stretching vibration absorption peak. The infrared spectrogram information proves that the synthesized compound is methacryloyloxyethyl dimethyl benzyl ammonium chloride (DMBAC).
As can be seen from FIG. 2, 3441cm-1，3394cm-1The absorption peak of the stretching vibration is 1659cm, which is the absorption peak of N-H in AM-1The peak of the absorption of stretching vibration is C ═ O. 1120cm-1Is a characteristic absorption peak of C-F bond stretching vibration at 1558cm-1，1506.16cm-1，1498cm-1And the positions are the vibration absorption peaks of the benzene ring framework, namely the characteristic absorption peaks of the DMBAC. The formation of the copolymer was observed from the infrared spectrum.
Example 2
(1) 2.5mol of acetone and1.5mol ofBenzyl chloride, slowly dripping 1mol of dimethylaminoethyl methacrylate at room temperature, stirring overnight, and filtering to obtain a white solid; washing with acetone for several times, and vacuum drying to obtain white powdery solid, namely methacryloyloxyethyl dimethyl benzyl ammonium chloride;
(2) in a three-neck flask with a stirrer and a spherical condenser, the mass ratio of the three-neck flask to the spherical condenser is 1: 5: 9: 34, adding hexafluorobutyl methacrylate, methacryloyloxyethyl dimethyl benzyl ammonium chloride, acrylamide and deionized water.
(3) Charging high-purity nitrogen into the reaction device, completely removing air in the reaction device after 1h, and heating and stirring.
(4) A mixed solution of potassium persulfate and sodium bisulfite (mass ratio: 3: 2) in an amount of 1.0% of the total mass of the monomers was added dropwise at 60 ℃ using a constant pressure dropping funnel. Heating and refluxing for reaction for 3 hours until the reaction viscosity is not changed any more, and stopping the reaction.
(5) Taking out the product, and mixing the product with a mixture of 1: 1, mixing the washing solution with ethanol and acetone until the solution is clear, putting the washed product into a vacuum oven for drying, and grinding the obtained product to obtain the final target product, namely the hydrophobic association type cationic polyacrylamide.
Example 3
(1) 2mol of acetone and2mol ofBenzyl chloride, slowly dripping 1.5mol of dimethylaminoethyl methacrylate at room temperature, stirring overnight, and filtering to obtain a white solid; washing with acetone for several times, and vacuum drying to obtain white powdery solid, namely methacryloyloxyethyl dimethyl benzyl ammonium chloride;
(2) in a three-neck flask with a stirrer and a spherical condenser, the mass ratio of the three-neck flask to the spherical condenser is 1: 7: 12: 30 percent of trifluoroethyl acrylate, methacryloyloxyethyl dimethylbenzyl ammonium chloride, acrylamide and deionized water.
(3) Charging high-purity nitrogen into the reaction device, completely removing air in the reaction device after 0.7h, heating and stirring.
(4) A potassium persulfate solution with a total monomer mass of 2.0% was added dropwise at 65 ℃ using a constant pressure dropping funnel. Heating and refluxing for reaction for 3.5 hours until the reaction viscosity is not changed any more, and stopping the reaction.
(5) Taking out the product, and mixing the product with a mixture of 1: 1, mixing the washing solution with ethanol and acetone until the solution is clear, putting the washed product into a vacuum oven for drying, and grinding the obtained product to obtain the final target product, namely the hydrophobic association type cationic polyacrylamide.
Example 4
(1) 1.2mol of acetone and1.3mol ofBenzyl chloride, slowly dripping 0.8mol of dimethylaminoethyl methacrylate at room temperature, stirring overnight, and filtering to obtain a white solid; washing with acetone for several times, and vacuum drying to obtain white powdery solid, namely methacryloyloxyethyl dimethyl benzyl ammonium chloride;
(2) in a three-neck flask with a stirrer and a spherical condenser, the mass ratio of the three-neck flask to the spherical condenser is 1: 5: 7: 25 of the weight percent, adding dodecafluoroheptyl acrylate, methacryloyloxyethyldimethylbenzylammonium chloride, acrylamide and deionized water.
(3) Charging high-purity nitrogen into the reaction device, completely removing air in the reaction device after 0.4h, heating and stirring.
(4) At 50 ℃, a constant pressure dropping funnel is used for dropping ammonium persulfate solution with the total mass of 2.5 percent of the monomers. Heating and refluxing for 4.5 hours until the reaction viscosity does not change any more, and stopping the reaction.
(5) Taking out the product, and mixing the product with a mixture of 1: 1, mixing the washing solution with ethanol and acetone until the solution is clear, putting the washed product into a vacuum oven for drying, and grinding the obtained product to obtain the final target product, namely the hydrophobic association type cationic polyacrylamide.
Example 5
(1) 1.4mol of acetone and1.8mol ofBenzyl chloride, slowly dripping 1.6mol of dimethylaminoethyl methacrylate at room temperature, stirring overnight, and filtering to obtain a white solid; washing with acetone for several times, and vacuum drying to obtain white powdery solid, namely methacryloyloxyethyl dimethyl benzyl ammonium chloride;
(2) in a three-neck flask with a stirrer and a spherical condenser, the mass ratio of the three-neck flask to the spherical condenser is 1: 6: 8: 35, adding dodecafluoroheptyl methacrylate, methacryloyloxyethyl dimethylbenzyl ammonium chloride, acrylamide and deionized water.
(3) Charging high-purity nitrogen into the reaction device, completely removing air in the reaction device after 0.2h, heating and stirring.
(4) At 70 ℃, a constant pressure dropping funnel is used for dropping ammonium persulfate solution with the total mass of 2.5 percent of the monomers. Heating and refluxing for reaction for 3.5 hours until the reaction viscosity is not changed any more, and stopping the reaction.
(5) Taking out the product, and mixing the product with a mixture of 1: 1, mixing the washing solution with ethanol and acetone until the solution is clear, putting the washed product into a vacuum oven for drying, and grinding the obtained product to obtain the final target product, namely the hydrophobic association type cationic polyacrylamide.
Example 6
(1) 1.3mol of acetone and2.3mol ofBenzyl chloride, slowly dripping 2.2mol of dimethylaminoethyl methacrylate at room temperature, stirring overnight, and filtering to obtain a white solid; washing with acetone for several times, and vacuum drying to obtain white powdery solid, namely methacryloyloxyethyl dimethyl benzyl ammonium chloride;
(2) in a three-neck flask with a stirrer and a spherical condenser, the mass ratio of the three-neck flask to the spherical condenser is 1: 4: 9: 35, adding dodecafluoroheptyl methacrylate, methacryloyloxyethyl dimethylbenzyl ammonium chloride, acrylamide and deionized water.
(3) Charging high-purity nitrogen into the reaction device, completely removing air in the reaction device after 0.5h, heating and stirring.
(4) At 40 ℃, a potassium persulfate-sodium sulfite mixed solution (mass ratio of 3: 2) which is 0.5 percent of the total mass of the monomers is dripped by using a constant pressure dropping funnel. Heating and refluxing for reaction for 3 hours until the reaction viscosity is not changed any more, and stopping the reaction.
(5) Taking out the product, and mixing the product with a mixture of 1: 1, mixing the washing solution with ethanol and acetone until the solution is clear, putting the washed product into a vacuum oven for drying, and grinding the obtained product to obtain the final target product, namely the hydrophobic association type cationic polyacrylamide.
Example 7
(1) 1.6mol of acetone and1.8mol ofBenzyl chloride, slowly dripping 2.2mol of dimethylaminoethyl methacrylate at room temperature, stirring overnight, and filtering to obtain a white solid; washing with acetone for several times, and vacuum drying to obtain white powdery solid, namely methacryloyloxyethyl dimethyl benzyl ammonium chloride;
(2) in a three-neck flask with a stirrer and a spherical condenser, the mass ratio of the three-neck flask to the spherical condenser is 1: 6: 12: 33, adding hexafluorobutyl acrylate, methacryloyloxyethyl dimethyl benzyl ammonium chloride, acrylamide and deionized water.
(3) Charging high-purity nitrogen into the reaction device, completely removing air in the reaction device after 1h, and heating and stirring.
(4) At the temperature of 80 ℃, a constant pressure dropping funnel is used for dropping ammonium persulfate-sodium thiosulfate mixed solution (the mass ratio is 3: 2) which is 3 percent of the total mass of the monomers. Heating and refluxing for 6 hours until the reaction viscosity does not change any more, and stopping the reaction.
(5) Taking out the product, and mixing the product with a mixture of 1: 1, mixing the washing solution with ethanol and acetone until the solution is clear, putting the washed product into a vacuum oven for drying, and grinding the obtained product to obtain the final target product, namely the hydrophobic association type cationic polyacrylamide.
Example 8
(1) 1mol of acetone and2.5mol ofBenzyl chloride, slowly dripping 2.5mol of dimethylaminoethyl methacrylate at room temperature, stirring overnight, and filtering to obtain a white solid; washing with acetone for several times, and vacuum drying to obtain white powdery solid, namely methacryloyloxyethyl dimethyl benzyl ammonium chloride;
(2) in a three-neck flask with a stirrer and a spherical condenser, the mass ratio of the three-neck flask to the spherical condenser is 1: 10: 15: adding trifluoroethyl methacrylate, methacryloyloxyethyl dimethyl benzyl ammonium chloride, acrylamide and deionized water according to the proportion of 40.
(3) Charging high-purity nitrogen into the reaction device, completely removing air in the reaction device after 0.5h, heating and stirring.
(4) A mixed solution of ammonium persulfate and sodium bisulfite (mass ratio: 3: 2) in an amount of 1.5% by mass of the total monomers was added dropwise at 55 ℃ using a constant pressure dropping funnel. Heating and refluxing for 4 hours until the reaction viscosity does not change any more, and stopping the reaction.
(5) Taking out the product, and mixing the product with a mixture of 1: 1, mixing the washing solution with ethanol and acetone until the solution is clear, putting the washed product into a vacuum oven for drying, and grinding the obtained product to obtain the final target product, namely the hydrophobic association type cationic polyacrylamide.
Example 9
(1) 3mol of acetone and0.5mol ofBenzyl chloride, 0.5mol of dimethylaminoethyl methacrylate is slowly dropped at room temperatureStirring overnight, and filtering to obtain white solid; washing with acetone for several times, and vacuum drying to obtain white powdery solid, namely methacryloyloxyethyl dimethyl benzyl ammonium chloride;
(2) in a three-neck flask with a stirrer and a spherical condenser, the mass ratio of the three-neck flask to the spherical condenser is 1: 10: 15: adding trifluoroethyl methacrylate, methacryloyloxyethyl dimethyl benzyl ammonium chloride, acrylamide and deionized water according to the proportion of 40.
(3) Charging high-purity nitrogen into the reaction device, completely removing air in the reaction device after 0.5h, heating and stirring.
(4) A mixed solution of ammonium persulfate and sodium bisulfite (mass ratio: 3: 2) in an amount of 1.5% by mass of the total monomers was added dropwise at 55 ℃ using a constant pressure dropping funnel. Heating and refluxing for 4 hours until the reaction viscosity does not change any more, and stopping the reaction.
(5) Taking out the product, and mixing the product with a mixture of 1: 1, mixing the washing solution with ethanol and acetone until the solution is clear, putting the washed product into a vacuum oven for drying, and grinding the obtained product to obtain the final target product, namely the hydrophobic association type cationic polyacrylamide.
The diatomite suspension simulated wastewater and oily wastewater were flocculated using the product prepared in example 1 of the present invention as a flocculant and compared with cationic polyacrylamide P (AM-DMC) and polyacrylamide PAM.
Surface tension and critical micelle concentration are important parameters for measuring surfactants. The surface tension of the polymer at different concentrations was measured by the hanging sheet method at room temperature. As can be seen from FIG. 3, as the mass concentration of the polymer increases, the surface tension of the aqueous solution gradually decreases, and the surface tension γ at the transition pointcmcThe surface activity of the polymer is 31.54mN/m, which shows that the polymer has higher surface activity, can effectively reduce the surface tension of water, and finally leads the oily wastewater to achieve oil-water separation.
Adding different concentrations of polymer P (AM-DMBAC-TFEMA), cationic polyacrylamide P (AM-DMC) and polyacrylamide PAM into the diatomite suspension at room temperature, fully stirring, standing for a period of time, taking supernatant, measuring the light transmittance and zeta potential of the supernatant on a spectrophotometer with the wavelength of 500nm, and inspecting the flocculation performance of the polymer.
As can be seen from FIG. 4, the polymers P (AM-DMBAC-TFEMA) and P (AM-DMC) have good removal effect on the diatomite suspension, and the transmittance of the supernatant can reach more than 90%. With the increase of the dosage, the permeability of the supernatant liquid is increased firstly and then reduced. When the dosage of P (AM-DMBAC-TFEMA) is 10mg/L, the transmittance can reach 99.28 percent. When the dosage of P (AM-DMC) is 20mg/L, the transmittance can reach 94.28%. It is clear that P (AM-DMBAC-TFEMA) has better flocculation performance than P (AM-DMC). Mainly because P (AM-DMBAC-TFEMA) contains benzene ring and fluorine-containing hydrophobic group, aggregation can occur in aqueous solution due to hydrophobicity, obvious hydrophobic association effect is shown, intermolecular association is generated on macromolecular chains, and large floccules are easy to form. The supernatant was somewhat clearer than the suspension without the polymer but still quite turbid with increasing amounts of PAM added. Mainly because PAM mainly plays a role in flocculation by adsorbing and bridging, and positive charge particles in the diatomite suspension cannot be neutralized by electricity and stably exist, and cannot be flocculated and settled.
As can be seen from FIG. 5, the suspension system of the diatomite solid particles is stable, mainly because the diatomite suspension particles are negatively charged, the particles have a larger zeta potential of-35.7 mv, and when P (AM-DMBAC-TFEMA) is added, the potential is rapidly reduced. While the potential was also reduced by adding PAM, there was no change. The diatomite adsorbs P (AM-DMC), and the charge conversion of P (AM-DMBAC-TFEMA) is mainly caused by the quaternary ammonium group-N on the chain nodes+(CH3)3Adsorption on diatomaceous earth changes the net charge on the surface, whereas PAM is mainly based on bridging and highly charged particles in suspension are stable and do not flocculate.
Adding a flocculating agent into the oily wastewater, uniformly stirring for 20min at room temperature at 200r/min, standing and settling, and taking the supernatant for later use.
As can be seen from FIG. 6, under the condition of 30 ℃ and 5h, the oil removal rate of P (AM-DMBAC-TFEMA) on the oily wastewater is obviously better than that of P (AM-DMC) and PAM (PAM) along with the increase of the polymer dosage, the oil removal rate is increased and then slowly reduced, and when the P (AM-DMBAC-TFEMA) dosage is 35mg/L, the oil removal rate reaches the maximum value of 95%. This is because when the amount of the polymer added is insufficient, the oil droplets cannot be sufficiently concentrated by adsorption-bridging and charge-neutralization to cause coagulation. When the addition amount is too large, the polymers are repelled to be dispersed and not to be stably coagulated, so that the oil removing effect is reduced.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent changes and modifications made within the scope of the present invention should be considered as the technical scope of the present invention.
Claims (8)
1. The application of the hydrophobic association type cationic polyacrylamide as a flocculating agent in removal of diatomite suspension is characterized in that the flocculating agent is obtained by reacting a reaction system containing a fluorine-containing monomer, methacryloyloxyethyl dimethylbenzyl ammonium chloride, acrylamide, deionized water and an initiator, wherein the mass ratio of the fluorine-containing monomer to the methacryloyloxyethyl dimethylbenzyl ammonium chloride to the acrylamide to the deionized water is 1: (1-10): (5-15): (15-40), wherein the initiator accounts for 0.5-3% of the total mass of the monomers;
the preparation method of the polyacrylamide comprises the following steps:
(1) adding a fluorine-containing monomer, methacryloyloxyethyl dimethyl benzyl ammonium chloride, acrylamide and deionized water into a reaction device provided with a stirrer and a spherical condenser pipe;
(2) filling nitrogen into the reaction device, completely removing air in the reaction device, and heating and stirring;
(3) when the temperature is raised to 40-80 ℃, an initiator is dripped to initiate polymerization reaction, and the reaction is stopped after heating reflux reaction until the reaction viscosity is not changed;
(4) taking out the product, and carrying out post-treatment to obtain the hydrophobic association type cationic polyacrylamide.
2. The use of claim 1, wherein the fluoromonomer is trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate or methacrylate.
3. Use according to claim 1, wherein the initiator is ammonium persulfate, potassium persulfate or a redox initiator; the oxidation-reduction initiator is ammonium persulfate-sodium sulfite, ammonium persulfate-sodium bisulfite, potassium persulfate-sodium sulfite, potassium persulfate-sodium bisulfite, ammonium persulfate-sodium thiosulfate or potassium persulfate-sodium thiosulfate.
4. The use according to claim 3, wherein the mass ratio of the oxidizing agent to the reducing agent in the redox initiation system is from 3: 2.
5. the use according to claim 3, wherein the methacryloyloxyethyldimethylbenzylammonium chloride is prepared by:
adding acetone and benzyl chloride into a container, slowly dripping dimethylaminoethyl methacrylate at room temperature, wherein the molar ratio of the acetone to the benzyl chloride to the dimethylaminoethyl methacrylate is (1-3): (0.5-2.5): (0.5-2.5), stirring overnight, and filtering to obtain a white solid; washing with acetone for several times, and vacuum drying to obtain white powder, i.e. methyl acryloyloxyethyl dimethyl benzyl ammonium chloride.
6. Use according to claim 3, wherein the nitrogen is liquid nitrogen or gaseous nitrogen.
7. The use according to claim 3, wherein the reaction time is 3-6h under heating and refluxing.
8. The use according to claim 3, wherein the post-processing step is specifically: using a mixture of 1: 1, mixing ethanol and acetone to wash the product until the solution is clear, putting the washed product into a vacuum oven to be dried, and then grinding.
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| CN103059219A (en) * | 2013-01-28 | 2013-04-24 | 重庆大学 | Preparation method for hydrophobic-association cationic polyacrylamide |
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| CN103059219A (en) * | 2013-01-28 | 2013-04-24 | 重庆大学 | Preparation method for hydrophobic-association cationic polyacrylamide |
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